EP0034527B1 - Fluor copolymers, their application to the hydrophobic and oleophobic treatment of different substrates, and substrates thus treated - Google Patents

Description

The subject of the invention is new fluorinated copolymers and their use for coating and impregnating various substrates such as textiles, leathers, wood, nonwovens, metals, concrete and, more particularly, papers and the like to make them. oleophobic and hydrophobic.

To obtain these properties, numerous fluorinated derivatives have already been proposed. However, if these derivatives have good properties on textiles and leather, it is necessary to obtain these same properties on paper and similar articles to use them at too high doses of active material (in this case the fluorine content linked to carbon) to obtain economically acceptable performance. As products more specially adapted to papers, chromium complexes have been proposed in French patents 1,172,664 and 2,022,351 and in US patent 3,907,576. These complexes which effectively confer advantageous oleophobic properties on papers and similar articles, however have the drawback of being colored green and of imparting this color to the substrates to which they are applied, thus limiting their use.

Polyfluoroalkyl or cycloalkyl phosphates have also been proposed for paper uses (French patents 1 305 612, 1 317 427, 1 388 621, 2055 551, 2 057 793 and 2 374 327, US patents 3 083 224 and 3 817 958, German patent 2,405,042) and hydroxypropyl polyfluoroalkyl phosphates (US Patent 3,919,361). However, these products which give papers good oleophobic properties, on the other hand, have the serious flaw of not giving them any hydrophobic properties. As a result, the papers treated with these products do not offer any protection against aqueous products. In addition, these products have no bonding power and even greatly reduce the effectiveness of the bonding agents, thus hampering the ability to write and print.

Have also been proposed for the treatment of papers and similar articles, copolymers of acrylic or methacrylic esters perfluoroaliphatic and acrylic or methacrylic esters of dialkylaminoalkyl, salified and N-oxidized (US Pat. No. 4,147,851). However, to give good oleophobic properties to the papers and similar articles to which they are applied, these copolymers must be used at high doses of active material; moreover, they confer only very weak hydrophobic properties. The same applies to the terpolymers described in US Pat. No. 4,127,711 based on perfluoroaliphatic acrylate or methacrylate, non-fluorinated polyethoxylated acrylate or methacrylate and dialkylaminoethyl acrylate or methacrylate.

It has now been found in the services of the applicant, new fluorinated products which, applied to paper and similar articles, give them at the same time, with a low rate of deposited fluorine, an excellent rate of sticking and very good properties hydrophobic and oleophobic, so that the papers and similar articles treated with these products have a real "barrier effect" against water and organic solvents, that is to say against the penetration of liquid aqueous or oily origin, fats and many organic solvents. Furthermore, applied to other very diverse substrates such as those mentioned above, these new products also give them very good oleophobic and hydrophobic properties.

• a) 35 à 98 %, de préférence 69 à 93 %, d'un ou plusieurs monomères polyfluorés de formule générale :
  
  dans laquelle Rf représente un radical perfluoro-alkyle à chaîne droite ou ramifiée, contenant 2 à 20 atomes de carbone, de préférence 4 à 16 atomes de carbone, Q représente un atome d'oxygène ou de soufre, B représente un enchaînement bivalent lié à Q par un carbone et pouvant comporter un ou plusieurs atomes d'oxygène, de soufre et/ou d'azote, l'un des symboles R représente un atome d'hydrogène et l'autre un atome d'hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone ;
• b) 1 à 15 %, de préférence 5 à 11 % et surtout 7 à 10 %, d'un ou plusieurs monomères de formule générale :
  
  dans laquelle B' représente un radical alkylène linéaire ou ramifié, contenant 1 à 4 atomes de carbone, R' représente un atome d'hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone, R₁ représente un radical alkyle contenant 1 à 18 atomes de carbone, hydroxyéthyle ou benzyle, R₂ représente un atome d'hydrogène ou un radical alkyle contenant 1 à 18 atomes de carbone, hydroxyéthyle ou benzyle ou R₁ et R₂ ensemble avec l'atome d'azote forment un radical morpholino, pipéridino ou pyrrolidinyle-1 ;
• c) 1 à 50 %, de préférence 2 à 20 %, d'un ou plusieurs monomères de formule générale :
  
  dans laquelle R₃, R'₃, R₄ et R₅ sont identiques ou différents et représentent chacun un atome d'hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone ; et éventuellement
• d) jusqu'à 10 %, de préférence moins de 5 %, d'un monomère quelconque autre que les monomères de formules (I), (II) et (III).

The products according to the invention are copolymers, optionally salified or quaternized, which comprise by weight:

• a) 35 to 98%, preferably 69 to 93%, of one or more polyfluorinated monomers of general formula:
  
  in which Rf represents a perfluoroalkyl radical with a straight or branched chain, containing 2 to 20 carbon atoms, preferably 4 to 16 carbon atoms, Q represents an oxygen or sulfur atom, B represents a bivalent chain linked to Q by a carbon and possibly comprising one or more oxygen, sulfur and / or nitrogen atoms, one of the symbols R represents a hydrogen atom and the other a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms;
• b) 1 to 15%, preferably 5 to 11% and especially 7 to 10%, of one or more monomers of general formula:
  
  in which B 'represents a linear or branched alkylene radical containing 1 to 4 carbon atoms, R' represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, R ₁ represents an alkyl radical containing 1 to 18 carbon, hydroxyethyl or benzyl atoms, R ₂ represents a hydrogen atom or an alkyl radical containing 1 to 18 carbon, hydroxyethyl or benzyl atoms or R ₁ and R ₂ together with the nitrogen atom form a morpholino radical, piperidino or pyrrolidinyl-1;
• c) 1 to 50%, preferably 2 to 20%, of one or more monomers of general formula:
  
  wherein R ₃ , R ' ₃ , R ₄ and R ₅ are the same or different and each represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms; and eventually
• d) up to 10%, preferably less than 5%, of any monomer other than the monomers of formulas (I), (II) and (III).

dans laquelle Rf et R ont les mêmes significations que ci-dessus, p représente un nombre entier allant de 1 à 20, de préférence égal à 2 ou 4, q représente un nombre entier allant de 1 à 4, de préférence égal à 1 ou 2, R₆ représente un atome d'hydrogène ou un radical alkyle contenant 1 à 10 atomes de carbone (de préférence méthyle), cycloalkyle contenant 5 à 12 atomes de carbone, hydroxyalkyle contenant 2 à 4 atomes de carbone ou aryle éventuellement substitué par un radical alkyle contenant 1 à 6 atomes de carbone, X, X', Y et Y' sont identiques ou différents et représentent chacun un atome d'hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone. Ces monomères peuvent être préparés suivant des procédés connus, par exemple par estérification des alcools correspondants de formule :

décrits dans le brevet français 2 034 142, au moyen d'un acide alcène-monocarboxylique de formule :

tel que, par exemple, l'acide acrylique, l'acide méthacrylique et l'acide crotonique, en présence de catalyseurs acides comme l'acide sulfurique ou l'acide p-toluènesulfonique. Au lieu des acides alcène- monocarboxyliques de formule (VI), on peut utiliser leurs esters, anhydrides ou halogénures. Pour des raisons économiques et pratiques, il s'est avéré particulièrement intéressant d'utiliser un mélange de monomères de formule (IV) présentant des radicaux Rf différents.As polyfluorinated monomers of formula (I), those corresponding to the formula are preferred:

in which Rf and R have the same meanings as above, p represents an integer ranging from 1 to 20, preferably equal to 2 or 4, q represents an integer ranging from 1 to 4, preferably equal to 1 or 2, R ₆ represents a hydrogen atom or an alkyl radical containing 1 to 10 carbon atoms (preferably methyl), cycloalkyl containing 5 to 12 carbon atoms, hydroxyalkyl containing 2 to 4 carbon atoms or aryl optionally substituted by a alkyl radical containing 1 to 6 carbon atoms, X, X ', Y and Y' are the same or different and each represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms. These monomers can be prepared according to known methods, for example by esterification of the corresponding alcohols of formula:

described in French patent 2,034,142, using an alkene-monocarboxylic acid of formula:

such as, for example, acrylic acid, methacrylic acid and crotonic acid, in the presence of acid catalysts such as sulfuric acid or p-toluenesulfonic acid. Instead of the alkene-monocarboxylic acids of formula (VI), their esters, anhydrides or halides can be used. For economic and practical reasons, it has proved particularly advantageous to use a mixture of monomers of formula (IV) having different Rf radicals.

dans lesquelles Rf et p ont les mêmes significations que ci-dessus, R₇ représente un atome d'hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone et r est un nombre entier allant de 1 à 20, de préférence 1 à 4.As other examples of polyfluorinated monomers of formula (I), mention may be made of the esters of acids of formula (VI) with alcohols and thiols of formulas:

in which Rf and p have the same meanings as above, R ₇ represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms and r is an integer ranging from 1 to 20, preferably 1 to 4 .

As examples of monomers of formula (II), there may be mentioned more particularly the acrylates and methacrylates of the following amino alcohols: 2-dimethylamino ethanol, 2-diethylamino ethanol, 2-dipropylamino-ethanol, 2-isobutylamino ethanol, N -tert-butyl amino-2 ethanol, N-tert-butyl N-methylamino-2 ethanol, morpholino-2 ethanol, N-methyl N-dodecylamino-2 ethanol, N-ethyl N-octadecylamino-2 ethanol, N-ethyl N - (2-ethylhexyl) 2-amino ethanol, 2-piperidino ethanol, (1-pyrrolidinyl) -2 ethanol, 3-diethylamino propanol-1, 2-diethylamino propanol-1, 1-dimethylamino-propanol-2, diethylamino-4 , butanol-1, diisobutylamino-4 butanol-1, dimethylamino-1 butanol-2, diethylamino-4 butanol-2. These esters can be prepared for example according to the method described in US Pat. No. 2,138,763.

As examples of monomers of formula (III), there may be mentioned more particularly N-vinyl pyrrolidone-2, N-vinyl methyl-3 pyrrolidone-2, N-vinyl methyl-4 pyrrolidone-2, N-vinyl methyl -5 pyrrolidone-2 and N-vinyl dimethyl-3,3 pyrrolidone-2, N-vinyl pyrrolidone-2 being preferred.

• - Les hydrocarbures oléfiniques inférieurs, halogénés ou non, tels que l'éthylène, le propylène, l'isobutène, le chloro-3 isobutène-1, le butadiène, l'isoprène, les chloro- et dichloro-butadiènes, les fluoro- et difluoro-butadiènes, le diméthyl-2,5 hexadiène-1,5, le diisobutylène ;
• - Les halogénures de vinyle, d'allyle ou de vinylidène tels que le chlorure de vinyle ou de vinylidène, le fluorure de vinyle ou de vinylidène, le bromure d'allyle, le chlorure de méthallyle ;
• - Le styrène et ses dérivés, tels que le vinyl-toluène, l'a-méthyl-styrène, l'a-cyanométhyl-styrène, le divinylbenzène, le N-vinyi carbazole ;
• - Les esters vinyliques tels que l'acétate de vinyle, le propionate de vinyle, les esters vinyliques des acides connus sur le marché sous le nom de « Versatic acids », l'isobutyrate de vinyle, le sénécioate de vinyle, le succinate de vinyle, l'isodécanoate de vinyle, le stéarate de vinyle, le carbonate de divinyle ;
• - Les esters d'allyle comme l'acétate d'allyle et l'heptanoate d'allyle ;
• - Les éthers alkyl-vinyliques ou alkyl-allyliques, halogénés ou non, tels que le cétyl vinyl éther, le dodécyl vinyl éther, l'isobutyl vinyl éther, l'éthyl vinyl éther, le chloro-2 vinyl éther, le tétra allyloxy éthane ;
• - Les vinyl alkyl cétones comme la vinyl méthyl cétone ;
• - Les acides insaturés, tels que les acides acrylique, méthacrylique, a-chloro-acrylique, crotonique, maléique, fumarique, itaconique, citraconique et sénécioïque, leurs anhydrides et leurs esters comme les acrylates et méthacrylates de vinyle, d'allyle, de méthyle, de butyle, d'isobutyle, d'hexyle, d'heptyle, d'éthyl-2 hexyle, de cyclohexyle, de lauryle, de stéaryle ou de cellosolve, le maléate de diméthyle, le crotonate d'éthyle, le maléate acide de méthyle, l'itaconate acide de butyle, les diacrylates et diméthacrylates de glycol ou de polyalkylène glycol, comme le diméthacrylate d'éthylène glycol ou de triéthylène glycol, les acrylates et méthacrylates de dichloro-phosphato alkyle comme le méthacrylate de dichloro-phosphato éthyle, ainsi que le phosphate acide de bis (méthacryloyloxy éthyle) ;
• - L'acrylonitrile, le méthacrylonitrile, le chloro-2 "acrylonitrile, l'acrylate de cyano-2 éthyle, le méthylène glutaronitrile, le cyanure de vinylidène, les cyano acrylates d'alkyle comme le cyano acrylate d'isopropyle, la trisacryloyl hexahydro-s-triazine, le vinyl trichlorosilane, le vinyl triméthoxysilane, le vinyl triéthoxysilane.

As other monomers (d) which can also be used in the context of the present invention, mention may be made of:

• - Lower olefinic hydrocarbons, halogenated or not, such as ethylene, propylene, isobutene, 3-chloro-isobutene-1, butadiene, isoprene, chloro- and dichloro-butadienes, fluoro- and difluoro-butadienes, 2,5-dimethyl-1,5-hexadiene, diisobutylene;
• - Vinyl, allyl or vinylidene halides such as vinyl or vinylidene chloride, vinyl or vinylidene fluoride, allyl bromide, methallyl chloride;
• - Styrene and its derivatives, such as vinyl toluene, a-methyl-styrene, a-cyanomethyl-styrene, divinylbenzene, N-vinyi carbazole;
• - Vinyl esters such as vinyl acetate, vinyl propionate, vinyl esters of acids known on the market under the name of "Versatic acids", vinyl isobutyrate, vinyl senecioate, vinyl succinate , vinyl isodecanoate, vinyl stearate, divinyl carbonate;
• - Allyl esters such as allyl acetate and allyl heptanoate;
• - Alkyl vinyl or alkyl allyl ethers, halogenated or not, such as cetyl vinyl ether, dodecyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-chloro vinyl ether, tetra allyloxy ethane ;
• - Vinyl alkyl ketones such as vinyl methyl ketone;
• - Unsaturated acids, such as acrylic, methacrylic, a-chloro-acrylic, crotonic, maleic, fumaric, itaconic, citraconic and senecioic acids, their anhydrides and their esters such as vinyl, allyl, methyl acrylates and methacrylates , butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, cyclohexyl, lauryl, stearyl or cellosolve, dimethyl maleate, ethyl crotonate, acid maleate methyl, butyl acid itaconate, diacrylates and dimethacrylates of glycol or polyalkylene glycol, such as ethylene glycol or triethylene glycol dimethacrylate, dichlorophosphato alkyl acrylates and methacrylates such as dichlorophosphato ethyl methacrylate, as well as bis (methacryloyloxy ethyl) acid phosphate;
• - Acrylonitrile, methacrylonitrile, 2-chloro-acrylonitrile, 2-cyano ethyl acrylate, methylene glutaronitrile, vinylidene cyanide, alkyl cyano acrylates such as isopropyl cyano acrylate, trisacryloyl hexahydro -s-triazine, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane.

May also be used as monomers (d), compounds having at least one ethylenic bond and at least one reactive group, that is to say a group capable of reacting with another monomer, another compound, or the substrate itself - even to establish cross-linking. These reactive groups are well known and can be polar groups or functional groups such as OH, NH _z , NH-alkyl, COOMe (Me = alkali or alkaline earth metal) groups,

As monomer of this type, mention may be made of hydroxyalkyl acrylates and methacrylates such as ethylene glycol monoacrylate, propylene glycol monomethacrylate, polyalkylene glycol acrylates and methacrylates, allyl alcohol, allyl glycolate, isobuteneneol, l allyloxy ethanol, o.allyl phenol, divinyl carbinol, glycerol a-allylether, acrylamide, methacrylamide, maleamide and maleimide, N- (cyanoethyl) -acrylamide, N-isopropylacrylamide, diacetone acrylamide , N- (hydroxy-methyl) acrylamide and methacrylamide, N- (alkoxymethyl) acrylamides and methacrylamides, glyoxal bis-acrylamide, sodium acrylate or methacrylate, vinyl sulfonic and styrene-p-sulfonic acids and their alkaline salts, 3-amino crotononitrile, monoallyl amine, vinyl pyridines, glycidyl acrylate or methacrylate, allyl glycidyl ether, acrolein.

The products according to the invention are prepared in a manner known per se by copolymerization of the monomers in solution in a solvent or in a mixture of solvents such as, for example, acetone, methyl ethyl ketone, γ-butyrolactone, methyl cyclohexanone, N-methyl pyrrolidone-2, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, diacetone alcohol, phenylmethylcarbinol, isophorone, tetrahydrofuran, dioxane, l ethyl acetate, glycol acetate, ethylene or polyethylene glycol monomethyl or monoalkylether, formamide, dimethylformamide, acetonitrile, toluene, trifluorotoluene, trichlorotrifluoroethane. Preferably, water-miscible solvents such as acetone and isopropyl alcohol are used.

The operation is carried out in the presence of suitable polymerization catalysts such as, for example, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, succinyl peroxide, azo-2,2 'bis-isobutyronitrile, azo -2.2 'bis- (2,4-dimethyl-4-methoxy valeronitrile), azo-4,4' bis- (4-cyano-pentanoic acid), azodicarbonamide, tert-butyl perpivalate. The amount of catalyst to be used can vary between 0.01 and 5%, preferably from 0.1 to 1.5%, relative to the total weight of the monomers used.

It is also possible to operate using a UV radiation source in the presence of photo-initiators such as benzophenone, 2-methyl anthraquinone or 2-chloro thioxanthone.

The reaction temperature can vary within wide limits, i.e. between room temperature and the boiling point of the reaction mixture. Preferably, one operates between 50 and 90 ° C.

If it is desired to adjust the molecular weight of the copolymers, it is possible to use chain transfer agents such as alkylmercaptans, such as tertio-dodecylmercaptan, n.dodecylmercaptan, n.octylmercaptan, carbon tetrachloride, triphenylmethane . The quantities to be used which are a function of the values which it is desired to obtain for the molecular weight, can vary from 0.01% to 3% relative to the total weight of the monomers and preferably between 0.05% and 0.5 %.

The optional salification of the copolymer can be done using strong or moderately strong mineral or organic acids, i.e. acids whose dissociation constant or the first dissociation constant is greater than 10- ⁵ . Mention may be made, for example, of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, formic acid, propionic acid. Preferably, acetic acid is used.

Instead of converting the copolymer into salt, it can be quaternized using an appropriate quaternizing agent such as, for example, methyl iodide, ethyl iodide, dimethyl sulphate, diethyl, benzyl chloride, trimethyl phosphate, methyl p-toluenesulfonate.

The solution of the copolymer obtained can optionally be diluted with the polymerization solvent or with another solvent or with a mixture of a solvent and water. If desired, the copolymer can also be isolated by removing the solvent (s).

As substrates capable of being made oleophobic and hydrophobic with the products according to the invention, mention may mainly be made of paper, cardboard and similar materials. Mention may also be made of other very diverse materials such as for example woven or non-woven articles based on cellulose or regenerated cellulose, natural, artificial or synthetic fibers such as cotton, cellulose acetate, wool, silk, polyamide, polyester, polyolefin, polyurethane or polyacrylonitrile fibers, leather, plastics, glass, wood, metals, porcelain, masonry, painted surfaces.

In the case of paper and cardboard, the solutions of the copolymers according to the invention are applied mainly in an aqueous medium, but also optionally in a solvent medium or in a mixture of water and solvents, according to known techniques, for example by coating , impregnation, immersion, spraying, brushing, padding, coating.

On paper and in aqueous solution, the products according to the invention can be applied either superficially on the support already finished, or in the mass, that is to say in the paper pulp or in the pulp.

The supports thus treated have good oleophobic and hydrophobic properties after a simple drying at room temperature or at a higher temperature, possibly followed by a heat treatment which can range depending on the nature of the support up to 250 ° C.

To obtain good fixation of the copolymers according to the invention on the substrates to which they are applied and to additionally give a particular effect, it is sometimes advantageous to combine them with certain adjuvants, polymers, thermo-condensable products and catalysts capable of promoting their crosslinking with the support. As such, there may be mentioned the condensates or precondensates of urea or melamine formaldehyde, methylol dihydroxyethylene urea and its derivatives, urones, methylol-ethylene-ureas, methylol-propylene-ureas, methylol-triazones, condensates of dicyandiamide-formaldehyde, methylol-carbamates, methylol-acrylamides or methacrylamides, their polymers or copolymers, divinyl sulfone, polyamides, epoxy derivatives such as diglycidyl glycerol, epoxypropyl trialkyl (aryl) ammonium halides such as chloride (2,3-epoxypropyl) trimethylammonium, N-methyl N- (2,3-epoxypropyl) morpholinium chloride, certain halogenated derivatives such as chloro-epoxypropane and dichloropropanol, or polar compounds such as the disodium salt of trisulfato-oxyethyl-sulfonium-betaine and the pyridinium salt of chloromethyl ether of ethylene glycol.

To evaluate the performance of the substrates treated according to the invention, the applicant has used the following tests:

Greaseproof test or "Kit value

This test described in Tappi, vol. 50, No. 10, pages 152A and 153A, standard RC 338 and UM 511, makes it possible to measure the greasiness of the substrates by mixtures of castor oil, toluene and heptane. These contain varying amounts of these three products:

The test consists in gently depositing drops of these mixtures on the treated paper. The drops are left on the paper for 15 seconds, then the appearance of the paper or cardboard is carefully observed and the wetting or penetration evidenced by browning of the surface is noted. The number corresponding to the mixture containing the highest percentage of heptane, which does not penetrate or wet the paper, is the “kit value” of the paper and is considered to be the oleophobicity rate of the treated paper. The higher the “kit value”, the better the oil repellency of the paper.

Turpentine test

This test is described in Tappi, standard T 454, ts 66 (1966).

On the test paper, itself placed on a white cardboard, are deposited 5 g of Fontainebleau sand washed with acids, then poured on the sand 1.1 ml of anhydrous turpentine colored with 0.5 g per liter of Rouge Organol B S. When the petrol is finished pouring, we start a stopwatch and move the paper every 30 seconds on the cardboard. We note the time elapsed when the card is stained. Beyond 30 minutes, it can be assumed that the test is no longer significant and that the substrate tested has excellent performance.

The test is carried out on 7 samples of the same paper. We note the values found from the smallest to the largest and we consider that the fourth value is the mean value.

Test measuring the “barrier to solvents” effect

In anhydrous turpentine and colored with 0.5 g / liter of Rouge Organol BS, a rectangular test tube (10 cm x 1 cm) of the substrate to be tested is immersed 1 cm in the lengthwise direction. This immersion is done in a closed cylindrical tank of 500 ml for a period of 24 hours. The surface of the spot formed by the rise of the colored liquid on the non-submerged portion of the substrate tested is then measured in mm ² .

Test measuring the “water barrier” effect

In a water colored with 0.5 g / liter of RHODAMINE B, a rectangular test tube (10 cm x 1 cm) of the substrate to be tested is immersed 3 cm lengthwise. This immersion is done in a closed cylindrical tank of 500 ml for a period of 24 hours. The surface of the spot formed by the rise of the colored liquid on the non-submerged portion of the substrate tested is then measured in mm ² .

COBB test

The COBB and LOWE test (Tappi Standard T441) codified by the Test Committee of the Central Laboratory of the Swedish Paper Industry (Project PCA 13-59) consists in measuring the weight (in g) of water absorbed for one minute by a square meter of paper supporting a water height of one centimeter.

Oleophobia test

On certain supports, the oleophobia was measured according to the method described in "AATCC Technical manual •, Test Method 118-1972, which evaluates the non-wettability of the substrate by a series of oily liquids whose surface tensions are more and more weak (Textil Research Journal, May 1969, page 451).

Hydrophobia test

On certain supports, the hydrophobicity was measured according to the method described in "AATCC Technical Manual", Test Method 22-1971.

The following examples in which the parts and percentages are by weight, unless otherwise stated, illustrate the invention without limiting it. In the application examples, a culture or expression rate of x% indicates the weight of the bath (x parts) retained by 100 parts of substrate.

Example 1

où n est égal à 3, 5, 7, 9, 11, 13 et 15 dans les rapports en poids moyens et respectifs de 1 : 50 : 31 : 10 : 3 : 1 : 1. On chauffe à 75 °C pendant 15 heures sous atmosphère d'azote, puis ajoute 160 parties d'eau, 250 parties d'alcool isopropylique et 8 parties d'acide acétique. On maintient encore pendant 2 heures à 75 °C, puis on refroidit jusqu'à température ambiante.In a reactor with a capacity of 1000 parts by volume, equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet and a heating device, 20 are charged. , 4 parts of acetone, 45 parts of isopropyl alcohol, 8 parts of dimethylaminoethyl methacrylate, 16 parts of N-vinyl-pyrrolidone, 0.8 part of azo-2,2 'bis-isobutyronitrile and 81.6 parts of a mixture of the polyfluorinated monomers of formula:

where n is equal to 3, 5, 7, 9, 11, 13 and 15 in the average and respective weight ratios of 1: 50: 31: 10: 3: 1: 1. It is heated at 75 ° C for 15 hours under a nitrogen atmosphere, then add 160 parts of water, 250 parts of isopropyl alcohol and 8 parts of acetic acid. It is still kept for 2 hours at 75 ° C., then cooled to room temperature.

563 parts of a solution (S ₁ ) of a copolymer according to the invention are thus obtained. This solution contains 18.8% non-volatile matter and its fluorine content is 6.6%.

Example 2

2a) In an apparatus identical to that of Example 1, 19.2 parts of acetone, 45 parts of isopropyl alcohol, 8 parts of dimethylaminoethyl methacrylate, 21 parts of N-vinyl-pyrrolidone are charged. part of azo-2,2 'bis-isobutyronitrile and 76.8 parts of the same mixture of polyfluorinated monomers as in Example 1. The mixture is heated at 75 ° C. for 15 hours under a nitrogen atmosphere, then 160 parts are added. of water, 250 parts of isopropyl alcohol and 8 parts of acetic acid. It is still kept for 2 hours at 75 ° C., then cooled to room temperature. 585 parts are thus obtained of a solution (S ₂ ) of a copolymer according to the invention. This solution contains 18.2% non-volatile matter and its fluorine content is 6%.

• A. Copolymère à base de 85 % du mélange de monomères polyfluorés tel que défini à l'exemple 1 et 15 % de méthacrylate de diméthylaminoéthyle, salifié et N-oxydé, préparé suivant l'exemple 1 du brevet US 4 147 851.
• B. Copolymère à base de 70 % du mélange de monomères polyfluorés tel que défini à l'exemple 1 et 30 % de méthacrylate de diméthylaminoéthyle, salifié et N-oxydé, préparé suivant l'exemple 2 du brevet US 4 147 851.
• C. Phosphate d'alcool polyfluoré de formule :
  
  décrit à l'exemple 5 du brevet français 1 317427.

2b) This copolymer and that obtained in Example 1 are tested at an equal fluorine content, compared to the following products:

• A. Copolymer based on 85% of the mixture of polyfluorinated monomers as defined in Example 1 and 15% of dimethylaminoethyl methacrylate, salified and N-oxidized, prepared according to Example 1 of US Pat. No. 4,147,851.
• B. Copolymer based on 70% of the mixture of polyfluorinated monomers as defined in Example 1 and 30% of dimethylaminoethyl methacrylate, salified and N-oxidized, prepared according to Example 2 of US Pat. No. 4,147,851.
• C. Polyfluorinated alcohol phosphate of formula:
  
  described in Example 5 of French patent 1 317427.

• - Composition fibreuse :
  • 60 % de pâte KRAFT blanchie à base de feuillus
  • 40 % de pâte KRAFT blanchie à base de résineux
• - Raffinage à l'hydrafineur 00 jusqu'à 35° SR
• - Adjuvants introduits :
  • talc : 15%
  • agent de rétention (RETAMINOL E de la Société BAYER) : 3 %
• - Poids du papier : 70 à 71 g/m²
• - Humidité du papier : 4 à 5 %.

These products are applied to unglued paper, the characteristics of which are as follows:

• - Fibrous composition:
  • 60% whitened hardwood KRAFT pulp
  • 40% KRAFT bleached softwood pulp
• - Refining with hydrafiner 00 up to 35 ° SR
• - Adjuvants introduced:
  • talc: 15%
  • retention agent (RETAMINOL E from BAYER): 3%
• - Paper weight: 70 to 71 g / m ²
• - Paper humidity: 4 to 5%.

To this end, five size-press baths are prepared, each containing 0.7 g of fluorine per liter and having the following composition (in g / liter):

Five sheets of unbonded paper are treated in size-press respectively in these five baths with an aging rate of 85%. After drying for 90 seconds at 110 ° C., papers are obtained having an anti-grease character, a "water barrier" effect and a "barrier to more or less strong solvents" effect. Their characteristics are grouped in the following table, compared to those of untreated paper.

Examination of the results of this table shows that the papers treated with the copolymers according to the invention (baths Nos. 1 and 2) not only have an excellent anti-grease character, but also exhibit “water barrier” effects. and “barrier to remarkable solvents.

2c) Five size-press baths are prepared, each containing 1 g of fluorine per liter and having the following composition (in g / liter):

Five sheets of AFNOR VII unbonded paper weighing 77 g / m ² are treated in size-press respectively with these five baths with a 95% rearing rate. After drying for 90 seconds at 110 ° C., the papers thus treated and an untreated paper are subjected to the COBB test.

The results are grouped in the following table:

Examination of the table shows that the papers treated with the copolymers according to the invention (baths ^S 6 and 7) have an excellent degree of bonding.

Example 3

In an apparatus identical to that of Example 1, 25 parts of acetone, 45 parts of isopropyl alcohol, 12 parts of dimethylaminoethyl methacrylate, 3 parts of N-vinyl-pyrrolidone, 0.4 part of nitrogen are charged. -2.2 'bis-isobutyronitrile and 100 parts of the same mixture of polyfluorinated monomers as in Example 1. The mixture is heated at 75 ° C. for 17 hours under a nitrogen atmosphere, then 165 parts of water, 250 parts are added. isopropyl alcohol and 8 parts acetic acid. It is still kept for 2 hours at 75 ° C., then cooled to room temperature. 589 parts of a solution (S ₃ ) of a copolymer according to the invention are thus obtained. This solution contains 19.1% non-volatile matter and its fluorine content is 7.8%.

• - Oléophobie (kit-value) 9
• - Test à l'essence de térébenthine supérieur à 30 minutes
• - Effet « barrière à l'eau » Surface de la tache 40 mm²
• - Effet « barrière aux solvants » Surface de la tache 10 mm²

Applied on the same paper and under the same conditions and proportions as in Example 2b (i.e. 9 g of solution S ₃ per liter of bath), this copolymer gives the paper the following characteristics:

• - Oleophobia (kit-value) 9
• - Turpentine test greater than 30 minutes
• - "Water barrier" effect Spot surface 40 mm ²
• - "Solvent barrier" effect Surface of the stain 10 mm ²

Example 4

In an apparatus identical to that of Example 1, 20.5 parts of acetone, 45 parts of isopropyl alcohol, 13 parts of dimethylaminoethyl methacrylate, 5 parts of N-vinyl-pyrrolidone, 0.8 part d are charged. 'azo-4,4' bis- (cyano pentanoic acid) and 82 parts of the same mixture of polyfluorinated monomers as in Example 1. The mixture is heated at 75 ° C. for 4 hours under a nitrogen atmosphere, then 160 parts are added. of water, 250 parts of isopropyl alcohol and 10 parts of acetic acid. It is still kept for 2 hours at 75 ° C., then cooled to room temperature. 580 parts of a solution (S ₄ ) of a copolymer according to the invention are thus obtained. This solution contains 17.2% of non-volatile matter and its fluorine content is 6.5%.

• - Oléophobie (kit-value) 9
• - Test à l'essence de térébenthine supérieur à 30 minutes

Applied on the same paper and under the same conditions and proportions as in Example 2b (i.e. 10.8 g of solution S ₄ per liter of bath), this copolymer gives the paper the following characteristics:

• - Oleophobia (kit-value) 9
• - Turpentine test greater than 30 minutes

Example 5

In an apparatus identical to that of example 1, 21.4 parts of acetone, 46 parts of isopropyl alcohol, 10 parts of dimethylaminoethyl methacrylate, 10 parts of N-vinyl-pyrrolidone, 0.8 part d are charged. 'azo-2,2' bis-isobutyronitrile and 85.6 parts of the same mixture of polyfluorinated monomers as in Example 1. The mixture is heated at 70 ° C. for 22 hours under a nitrogen atmosphere, then 160 parts of water, 250 parts of isopropyl alcohol and 10 parts of acetic acid. It is still kept for one hour at 70 ° C, then cooled to room temperature. 530 parts of a solution (S _s ) of a copolymer according to the invention are thus obtained. This solution contains 19.1% non-volatile matter and its fluorine content is 7.1%.

By mixing 0.42 g of the solution S ₅ , 4 g of a dry "bleached bisulfite" paste and 156 g of water, an aqueous paste is prepared containing 0.03 g of fluorine. This paste is then diluted with 4 liters of water in the bowl of a "Rapid-Kotten" machine. The mixture is stirred for 30 seconds, then filtered under vacuum. The paper sheet thus obtained is dried under vacuum for 10 minutes at 90 ° C. on the plates of the "Rapid-Kotten" machine. Finally, a mass-treated sheet of paper is obtained, the characteristics of which appear in the following table, compared with those of an untreated control sheet.

(See table p. 11)

Example 6

Preparing a padding bath consisting of 40 parts of the solution Si according to Example 1, 40 parts of an aqueous solution at 65% of a precondensate of trimethyl ether of hexamethylolmelamine, 4 parts of lactic acid and 916 parts of water. Three fabrics of different composition: an acrylic fiber fabric (DRALON), a polyester fiber fabric (TERGAL) and a mixed polyester-cotton fabric 66/33, are used in this bath with respective expression rates of 112% , 87% and 70%. The tissues are then treated for 3 minutes at 165 ° C. in a BENZ thermocondenser.

The characteristics of the tissues thus treated (T) are indicated in the following table, compared with those of the untreated control tissues (NT).

Examination of the results in the table above shows that the fabrics finished with the copolymers according to the invention have an anti-stain character, that is to say are capable of withstanding lean and oily stains.

Example 7

On two different leathers, 100 g / m ² of the solution S2 according to Example 2a is applied by brush and allowed to dry for 24 hours at room temperature. Leathers are obtained which have remarkable oleophobic and hydrophobic properties, as shown by the characteristics indicated in the following table.

Example 8

In an apparatus identical to that of Example 1, 21.4 parts of acetone, 90 parts of isopropyl alcohol, 8 parts of dimethylaminoethyl methacrylate, 12 parts of N-vinyl-pyrrolidone, 0.8 part d are charged. 'azo-4,4' bis- (4-cyano-pentanoic acid) and 85.6 parts of the polyfluorinated monomer of formula:

The mixture is heated at 70 ° C. for 10 hours under a nitrogen atmosphere, then 160 parts of water, 205 parts of isopropyl alcohol and 5 parts of acetic acid are added. It is kept for two hours at 70 ° C, then cooled to room temperature. 580 parts of a solution (Sa) of a copolymer according to the invention are thus obtained. This solution contains 17.6% non-volatile matter and its fluorine content is 6.5%.

• - Oléophobie (kit-value) 9
• - Test à l'essence de térébenthine supérieur à 30 minutes

Applied on the same paper and under the same conditions and proportions as in Example 2b (i.e. 10.8 g of solution S ₆ per liter of bath), this copolymer gives the paper the following characteristics:

• - Oleophobia (kit-value) 9
• - Turpentine test greater than 30 minutes

Example 9

Using a brush, an oak wood board is coated with 100 g / m ² of the solution S ₅ described in Example 5 and left to dry for 24 hours at room temperature.

The hydrophobic effect of the support thus treated is measured by depositing on the surface of the wood a few drops of each of the following 7 solutions:

The rating corresponds to the number of the solution richest in isopropyl alcohol which does not wet not the support. This wetting is evidenced by total penetration of the liquid or by browning of the surface in contact with the liquid.

The oleophobic effect is measured using the solutions of the AATCC 118-1972 standard. A few drops of each of the solutions are placed on the surface of the wood. The rating corresponds to the number of the lowest surface tension solution, which does not penetrate the support or for which no browning of the surface in contact with the liquid is observed.

Compared to untreated wood, the characteristics are as follows:

Example 10

In an apparatus identical to that of Example 1, 14.2 parts of acetone, 45 parts of isopropyl alcohol, 3 parts of dimethylaminoethyl methacrylate, 40 parts of N-vinyl-pyrrolidone, 0.8 part d are charged. 'azo-4,4' bis- (4-cyano-pentanoic acid) and 56.8 parts of the same mixture of polyfluorinated monomers as in Example 1. The mixture is heated at 80 ° C. for 4 hours under a nitrogen atmosphere, then 160 parts of water, 160 parts of isopropyl alcohol and 2 parts of acetic acid are added. It is still kept for one hour at 80 ° C., then cooled to room temperature. 460 parts of a solution (S ₇ ) of a copolymer according to the invention are thus obtained. This solution contains 21.2% non-volatile matter and its fluorine content is 5.5%.

• - Oléophobie (kit-value) 9
• - Test à l'essence de térébenthine supérieur à 30 minutes

Applied on the same paper and under the same conditions as in Example 2b, but at the rate of 0.8 g of fluorine per liter of bath (i.e. 14.5 g of solution S ₇ per liter of bath), this copolymer gives paper the following characteristics:

• - Oleophobia (kit-value) 9
• - Turpentine test greater than 30 minutes

Example 11

In an apparatus identical to that of Example 1, 45 parts of isopropyl alcohol are charged, 4 parts of dimethylaminoethyl methacrylate, 6 parts of N-vinyl-pyrrolidone, 0.4 part of 4,4 'azo acid bis- (4-cyano-pentanoic) and 40 parts of the polyfluorinated monomer of formula:

The mixture is heated at 70 ° C. for 24 hours under a nitrogen atmosphere, then 80 parts of water, 100 parts of isopropyl alcohol and 2 parts of acetic acid are added. It is kept for another hour at 80 ° C. and then cooled to ambient temperature. 275 parts of a solution (Sa) of a copolymer according to the invention are thus obtained. This solution contains 17.8% non-volatile matter and its fluorine content is 8.8%.

In a padding bath composed of 10 parts of the solution (Se) and 990 parts of water, a nonwoven (dry process) of polyester weighing 200 g / m ² is padded with a rate of expression of 250%, then dried for 3 minutes at 165 ° C in a BENZ thermocondenser.

The characteristics of the nonwoven thus treated are indicated in the following table, compared with an untreated control nonwoven. ,

(See table p. 14)

Example 12

In an apparatus identical to that of Example 1, 21.3 parts of acetone, 45 parts of isopropyl alcohol, 14 parts of dimethylaminoethyl methacrylate, 1 part of N-vinyl-pyrrolidone, 0.8 part d are charged. 'azo-4,4' bis- (4-cyano-pentanoic acid) and 85 parts of the polyfluorinated monomer of formula:

The mixture is heated at 70 ° C. for 6 hours under a nitrogen atmosphere then 160 parts of water, 160 parts of isopropyl alcohol and 8 parts of acetic acid. It is still kept for one hour at 70 ° C, then cooled to room temperature. 490 parts of a solution (Sg) of a copolymer according to the invention are thus obtained. This solution contains 20% non-volatile matter and its fluorine content is 7.8%.

In a padding bath composed of 10 parts of Sg solution and 990 parts of water, a cellulosic nonwoven (wet) weighing 46 g / m ² , is padded, with a rate of expression of 150%, then dried for 3 minutes at 165 ° C in a BENZ thermocondenser.

The characteristics of the nonwoven thus treated are indicated in the following table, compared with an untreated control nonwoven.

Example 13

In an apparatus identical to that of Example 1, 20.4 parts of acetone, 45 parts of isopropyl alcohol, 6 parts of dimethylaminoethyl methacrylate, 16 parts of N-vinyl-pyrrolidone, 2 parts of monomethacrylate are charged. ethylene glycol, 0.8 part of azo-4,4 'bis- (4-cyano-pentanoic acid) and 81.6 parts of the same mixture of polyfluorinated monomers as in Example 1. The mixture is heated to 80 ° C. for 4 hours under a nitrogen atmosphere, then add 160 parts of water, 250 parts of isopropyl alcohol and 6 parts of acetic acid. It is still kept for 2 hours at 80 ° C., then cooled to room temperature. 583 parts of a solution (S _io ) of a copolymer according to the invention are thus obtained. This solution contains 18.1% non-volatile matter and its fluorine content is 6.4%.

• - Oléophobie (kit-value) 9
• - Test à l'essence de térébenthine supérieur à 30 minutes

Applied on the same paper and under the same conditions and proportions as in Example 2b (i.e. 11 g of solution S ₁₀ per liter of bath), this copolymer gives the paper the following characteristics:

• - Oleophobia (kit-value) 9
• - Turpentine test greater than 30 minutes

Example 14

In an apparatus identical to that of Example 1, 18.4 parts of acetone, 50 parts of isopropyl alcohol, 8 parts of tert-butylaminoethyl methacrylate, 16 parts of N-vinyl-pyrrolidone, 0.8 part of azo-4,4 'bis- (4-cyano-pentanoic acid) and 73.6 parts of the same mixture of polyfluorinated monomers as in Example 1. The mixture is heated at 80 ° C. for 6 hours under an atmosphere of nitrogen, then add 160 parts of water, 250 parts of isopropyl alcohol and 4 parts of acetic acid. It is still kept for one hour at 80 ° C., then cooled to room temperature. 560 parts of a solution (S ₁₁ ) of a copolymer according to the invention are thus obtained. This solution contains 17.3% non-volatile matter and its fluorine content is 6%.

• - Oléophobie (kit-value) 9
• - Test à l'essence de térébenthine supérieur à 30 minutes

Applied on the same paper and under the same conditions as in Example 2b (i.e. 11.6 g of Sn solution per liter of bath), this copolymer gives the paper the following characteristics:

• - Oleophobia (kit-value) 9
• - Turpentine test greater than 30 minutes

Example 15

In an apparatus identical to that of Example 1, 18.7 parts of acetone, 50 parts of isopropyl alcohol, 12 parts of dimethylaminoethyl methacrylate, 10 parts of N-vinyl-pyrrolidone, 6 parts of acetate are charged of vinyl, 0.8 part of azo-4,4 'bis- (4-cyano-pentanoic acid) and 74.7 parts of the same mixture of polyfluorinated monomers as in Example 1. The mixture is heated at 80 ° C. for 6 hours under nitrogen, then add 160 parts of water, 250 parts of isopropyl alcohol and 12 parts of acetic acid. It is further maintained at 80 ° C for one hour, then cooled to room temperature. ' 572 parts of a solution (S ₁₂ ) of a copolymer according to the invention are thus obtained. This solution contains 17.6% non-volatile matter and its fluorine content is 5.9%.

• - Oléophobie (kit-value) 9
• - Test à l'essence de térébenthine supérieur à 30 minutes

Applied on the same paper and under the same conditions as in Example 2b (i.e. 11.8 g of solution S ₁₂ per liter of bath), this copolymer gives the paper the following characteristics:

• - Oleophobia (kit-value) 9
• - Turpentine test greater than 30 minutes

Claims (9)

1. Fluorinated copolymers, if necessary salified or quaternised, characterised by the fact that they comprise :

a) 35 to 98 % by weight of one or more polyfluorinated monomers of general formula :

in which Rf represents a perfluoro-alkyl radical with straight of branched chain, containing 2 to 20 carbon atoms, Q represents an atom of oxygen or sulphur, B represents a bivalent linkage connected to Q by a carbon and capable of including one or more atoms of oxygen, sulphur and/or nitrogen, one of the symbols R represents an atom of hydrogen and the other an atom of hydrogen or an alkyl radical containing 1 to 4 carbon atoms ;

b) 1 to 15 % by weight of one or more monomers of general formula :

in which B' represents a linear or branched alkylene radical containing 1 to 4 carbon atoms, R' represents an atom of hydrogen or an alkyl radical containing 1 to 4 carbon atoms, R₁ represents an alkyl radical containing 1 to 18 carbon atoms, hydroxyethyl or benzyl, R₂ represents an atom of hydrogen or an alkyl radical containing 1 to 18 carbon atoms, hydroxyethyl or benzyl, or R₁ and R₂ together with the nitrogen atom form a morpholino, piperidino or 1-pyrrolidinyl radical ;

c) 1 to 50 % by weight of one or more monomers of general formula :

in which R₃, R'₃, R₄ and R₅ are identical or different and each represents an atom of hydrogen or an alkyl radical containing 1 to 4 carbon atoms ; and as appropriate

d) up to 10 % by weight of a monomer which is any other than the monomers of formulae (i), (II), and (III).

2. Copolymers according to Claim 1, comprising 69 to 93 % by weight of polyfluorinated monomer(s) of formula (I), 5 to 11 % by weight of monomer(s) of formula (II), 2 to 20 % by weight of monomer(s) of formula (III) and 0 to 5% by weight of another monomer.

3. Copolymers according to claim 2, comprising 7 to 10 % of monomer(s) of formula (II).

4. Copolymers according to one of the claims 1 to 3, in which the polyfluorinated monomer or monomers correspond(s) to the formula :

in which Rf and R have the same significance as in Claim 1, p represents a whole number between 1 and 20, preferably equal to 2 or 4, q represents a whole number between 1 and 4, preferably equal to 1 or 2, R₆ represents an atom of hydrogen or an alkyl radical containing 1 to 10 carbon atoms, a cycloalkyl radical containing 5 to 12 carbon atoms, a hydroxyalkyl radical containing 2 to 4 carbon atoms, or an aryl radical, substituted as appropriate by an alkyl radical containing 1 to 6 carbon atoms, X, X', Y and Y' are identical or different and each represents an atom of hydrogen or an alkyl radical containing 1 to 4 carbon atoms.

5. Copolymers according to Claim 4, obtained from a mixture of monomers of formula (IV) which have different Rf radicals.

6. Copolymers according to one of the claims 1 to 5, in which the monomer of formula (II) is dimethylaminoethyl methacrylate.

7. Copolymers according to one of the claims 1 to 6, in which the monomer of formula (III) is N-vinyl 2-pyrrolidone.

8. The application of the copolymers according to one of the claims 1 to 7, for the oil-proofing and water-proofing of various substrates, in particular, papers, cartons and similar articles.

9. The materials and articles treated by means of a copolymer according to one of the claims 1 to 7.